Layered product

ABSTRACT

A laminated product is provided which has no problems concerning hygienic safety or environment accompanying the use of solvent-based adhesives and which has been tenaciously bonded in a degree equal or superior to that attainable with conventional CR solvent-based adhesives. The laminated product is obtained by bonding a porous organic material and a cloth with an adhesive comprising, as major ingredients, a polychloroprene latex which is obtained by polymerizing 100 parts by mass of chloroprene with more than 0 part by mass and less than 2 parts by mass of an ethylenically unsaturated carboxylic acid in the presence of from 0.5 to 4 parts by mass of a polyvinyl alcohol and then adding a pH adjustor and a radical scavenger and which has a gel content in the chloroprene polymer of from 10 to 60 mass % and a pH of from 6 to 10, a tackifier resin and a metal oxide.

TECHNICAL FIELD

[0001] The present invention relates to a laminated product which isuseful as a component required to have cushioning or impact-absorbingproperties, of e.g. furniture, bed clothes, interior parts ofautomobiles, shoe materials such as shoe soles or inner soles of e.g.sports shoes, walking shoes or sandals, health care equipments,clothing, wet suits or packaging materials.

BACKGROUND ART

[0002] Heretofore, polychloroprene (hereinafter referred to as CR)solvent-based adhesives have been used to prepare laminated products fore.g. shoe soles or inner soles of e.g. sports shoes or walking shoes.

[0003] However, in such CR solvent-based adhesives, an organic solventsuch as toluene, ethyl acetate or methyl ethyl ketone is used, and suchan organic solvent will evaporate at the work area during the coatingoperation of the adhesive, such being undesirable from the viewpoint ofhygienic safety of workers or environment. Accordingly, it has beendesired to reduce the organic solvent.

[0004] It is an object of the present invention to provide a laminatedproduct which has no problems concerning hygienic safety or environmentaccompanying the use of the conventional CR solvent-based adhesives andwhich has been tenaciously bonded in a degree equal or superior to thatattainable by the conventional CR solvent-based adhesives.

DISCLOSURE OF THE INVENTION

[0005] As a result of an extensive study to accomplish the above object,the present inventors have invented a sufficiently bonded laminatedproduct by coating an adhesive composition (hereinafter sometimes simplyreferred to as an adhesive) comprising, as major ingredients, apolychloroprene latex which is obtained by polymerizing 100 parts bymass of chloroprene with more than 0 part by mass and less than 2 partsby mass of an ethylenically unsaturated carboxylic acid in the presenceof from 0.5 to 4 parts by mass of a polyvinyl alcohol and then adding apH adjustor and a radical scavenger and which has a gel content in thechloroprene polymer of from 10 to 60 mass % and a pH of from 6 to 10, atackifier resin and a metal oxide.

[0006] Namely, the present invention provides a laminated productexcellent in the bond strength and the water resistant bond strengthhaving a porous organic material and a cloth bonded with an adhesivecomprising, as major ingredients, a polychloroprene latex which isobtained by polymerizing 100 parts by mass of chloroprene with more than0 part by mass and less than 2 parts by mass of an ethylenicallyunsaturated carboxylic acid in the presence of from 0.5 to 4 parts bymass of a polyvinyl alcohol and then adding a pH adjustor and a radicalscavenger and which has a gel content in the chloroprene polymer of from10 to 60 mass % and a pH of from 6 to 10, a tackifier resin and a metaloxide.

[0007] Now, the present invention will be described in detail. In thepresent invention, the cloth is woven fabric, knitted fabric ornon-woven fabric, and the material of fibers, texture, thread count,(T+W) density (T represents warp and W represents weft), thickness andproduction method are not limited and may be selected in considerationof the texture and color depending upon the particular purpose orapplication. The woven fabric may, for example, be a spun woven fabricand a filament woven fabric, and the fiber material may, for example, becotton, silk, rayon, cupola, acetate, triacetate, nylon, polyester,acryl or promix. The knitted fabric may also be called knit goods, knitor jergy cloth, and the fiber material may, for example, be cotton,silk, rayon, cupola, acetate, triacetate, nylon, polyester, acryl orpromix. The non-woven fabric may, for example, be a wet system non-wovenfabric, a chemical bonded non-woven fabric, a thermal bonded non-wovenfabric, an air laid non-woven fabric, a spun lace non-woven fabric, aspun bonded non-woven fabric, a meltblown non-woven fabric, a needlepunched non-woven fabric or a stitch bonded non-woven fabric, and thefiber material may, for example, be cotton, rayon, polyester,polypropylene, nylon, acryl, vinylon, glass fiber, pulp or carbon fiber.

[0008] In the present invention, the porous organic material is meantfor a foamed plastic or a foamed rubber (foam rubber). The foamingmethod, or the material or thickness of the foamed product, is notparticularly limited and may be selected in consideration of theflexibility or the strength of the material depending upon theparticular purpose or application.

[0009] The foaming method may, for example, be melt foaming, solid phasefoaming or cast foaming. A specific example of the melt foaming may bechemical crosslinking foaming, electron beam crosslinking foaming,extrusion foaming, one step press foaming or two step press foaming. Aspecific example of the solid phase foaming may be a beads method. Thecast foaming may, for example, be molding foaming, block foaming (slabfoaming), continuous laminate foaming, injection foaming or sprayfoaming.

[0010] Further, the material may, for example, be a flexible foamedurethane (flexible foamed PUR), a foamed polypropylene (foamed PP), afoamed polyethylene (foamed PE), a foamed ethylene/vinyl acetatecopolymer (foamed EVA), a foamed vinyl chloride (foamed PVC) or a foamedpolychloroprene (foamed CR). Among them, flexible foamed PUR, foamed PPor foamed EVA which is excellent in processability by thermoforming ispreferred. Particularly preferred is foamed PP having a density of from10 to 80 kg/m³ before press bonding, or foamed EVA having a density offrom 70 to 120 kg/m³ before press bonding. Within such a density range,the bonding can be made more tenacious. Among them, foamed EVA isparticularly preferred since not only tenacious bonding will thereby bepossible, but also molding will be easy.

[0011] Here, the density is the mass per unit volume of a material at23° C. and is obtained by determining the volume by measuring the sizeof a rectangular parallel-piped material by a pair of calipers and bymeasuring the mass by a weighing apparatus.

[0012] The thickness of the porous organic material is not particularlylimited and may be selected depending upon the particular purpose orapplication. For example, in consideration of an application to innersoles for sports shoes, the thickness is preferably at most 10 mm.Further, such a porous organic material may be one having another sheetlaminated on such a sheet, so long as the bond surface is made of theabove-mentioned porous organic material.

[0013] A specific example of the ethylenically unsaturated carboxylicacid in the present invention may be acrylic acid, methacrylic acid,crotonic acid, fumaric acid, maleic acid, citraconic acid or grutaconicacid. These may be used alone or in combination as a mixture of two ormore of them. In the present invention, it is preferred to use acrylicacid or methacrylic acid, and it is particularly preferred to usemethacrylic acid.

[0014] Further, the amount of the ethylenically unsaturated carboxylicacid to be added in the present invention is more than 0 part by massand less than 2 parts by mass, preferably from 0.7 to 1.5 parts by mass,per 100 parts by mass of chloroprene. If the amount of the ethylenicallyunsaturated carboxylic acid is 0 part by mass, the stability of thelatex will be poor, whereby the production tends to be difficult, or thebond strength in a normal state will be poor. If the amount of theethylenically unsaturated carboxylic acid is 2 or more parts by mass,the decrease of the water resistant bond strength will be substantial.

[0015] Further, the chloroprene polymer to be used in the presentinvention may have a small amount of copolymerizable another monomercopolymerized in addition to chloroprene and the ethylenicallyunsaturated carboxylic acid, and such a polymer is also included in thepresent invention.

[0016] In the present invention, the monomer copolymerizable withchloroprene may, for example, be 2,3-dichloro-1,3-butadiene,1-chloro-1,3-butadiene, butadiene, isoprene, styrene, acrylonitrile, anester of acrylic acid or an ester of methacrylic acid, and two or moretypes may be used in combination, as the case requires.

[0017] In the present invention, the polyvinyl alcohol is notparticularly limited, but one having a saponification degree within arange of from 60 to 98 mol %, is preferred. More preferably, thesaponification degree is from 75 to 95 mol %, and further preferably,the saponification degree is from 75 to 90 mol %.

[0018] Further, the polyvinyl alcohol is preferably one having apolymerization degree within a range of from 200 to 3000. Morepreferably, the polymerization degree is from 200 to 700.

[0019] When the polyvinyl alcohol is within this range, thepolymerization operation can be carried out constantly, and thestability of the obtained latex will be excellent, and it will bepossible to obtain a stable latex at a high solid content.

[0020] In the present invention, the polyvinyl alcohol is addedpreferably in an amount of from 0.5 to 4 parts by mass, more preferablyfrom 2 to 4 parts by mass, further preferably from 3 to 3.5 parts bymass, per 100 parts by mass of chloroprene. If the amount of thepolyvinyl alcohol added is less than 0.5 part by mass, the emulsifyingpower tends to be inadequate, whereby agglomerates are likely to beformed during the polymerization reaction. On the other hand, if itexceeds 4 parts by mass, the viscosity tends to increase during thepolymerization reaction, whereby stirring tends to be impaired, orabnormal heat generation may result, whereby the production maysometimes become difficult.

[0021] Further, the polychloroprene latex in the present invention isrequired to have a toluene-insoluble gel content within a range of from10 to 60 mass %, preferably within a range of from 15 to 60 mass %. Ifthe gel content is less than 10 mass %, the bond strength in a normalstate tends to be low. On the other hand, if the gel content exceeds 60mass %, the initial adhesion tends to deteriorate, and the waterresistant bond strength tends to be low.

[0022] The gel content of the polychloroprene latex can be controlled bycontrolling {circle over (1)} the type and the amount of a chaintransfer agent to be used, {circle over (2)} the polymerizationtemperature, and {circle over (3)} the polymerization rate.

[0023] Firstly, the chain transfer agent is not particularly limited solong as it is one commonly used for the production of a polychloroprene,and for example, it is possible to use a known chain transfer agent,such as a long chain alkyl mercaptan such as n-dodecylmercaptan,n-octadecylmercaptan or tert-dodecylmercaptan, a dialkylxanthogendisulfide such as diisopropylxanthogen disulfide or diethylxanthogendisulfide, or iodoform.

[0024] Next, the polymerization temperature is preferably within a rangeof from 0 to 55° C. from the viewpoint of the control of thepolymerization. In order to carry out the polymerization reactionsmoothly and safely, it is particularly preferred to adjust thepolymerization temperature within a range of from 30 to 50° C.

[0025] Further, the final polymerization rate is preferably at least 80mass %, more preferably at least 90 mass %.

[0026] In the present invention, the solid content concentration of thepolychloroprene latex can be adjusted to a necessary concentration byconcentration or dilution with water, but it is preferably within arange of from 40 to 65 mass %, more preferably within a range of from 43to 58 mass %. By adjusting it to have a higher solid contentconcentration, it will be a latex having a high drying speed and beingexcellent in the initial adhesion. Further, the solid contentconcentration can be adjusted also by the ratio of monomers at the timeof polymerization, but it can also be adjusted by carrying outconcentration after the polymerization.

[0027] The chloroprene polymer in the present invention is acidic and inan unstable state immediately after the polymerization, and accordingly,it is necessary to adjust the pH to from 6 to 10. Preferably, the pH isfrom 6.5 to 9.0. If the pH is less than 6, coagulation, or separationand property change is likely to take place for a long period ofstorage. On the other hand, an alkaline solution having a pH exceeding10 is not desirable from the viewpoint of safety in handling.

[0028] As the PH adjustor in the present invention, it is preferred tocontain a weakly acidic salt such as sodium carbonate, potassiumcarbonate, trisodium phosphate, disodium hydrogenphosphate, tripotassiumphosphate, dipotassium hydrogenphosphate, tripotassium citrate,dipotassium hydrogencitrate, trisodium citrate, disodiumhydrogencitrate, sodium acetate, potassium acetate or sodium tetraboratein an amount of at least 0.1 part by mass, more preferably at least 0.3part by mass, per 100 parts by mass of the solid content of thepolychloroprene latex. The weakly acidic salt is required to increasethe buffering ability of the polychloroprene latex, and if it is lessthan 0.1 part by mass, the pH decrease during the storage cannot besuppressed, whereby the storage stability of the adhesive compositiondeteriorates. In a case where the pH of the polychloroprene latex willnot reach 6 by the weakly acidic salt only, a basic substance such assodium hydroxide, potassium hydroxide or diethanolamine, may optionallybe used in combination.

[0029] In the present invention, the method for adding the PH adjustoris not particularly limited, and a powder of the PH adjustor may beadded directly or after diluting it to an optional proportion withwater.

[0030] The radical scavenger in the present invention may be apolymerization inhibitor such as thiodiphenylamine,diethylhydroxylamine, hydroquinone, p-t-butylcatechol,1,3,5-trihydroxybenzene or hydroquinone methyl ether or an antioxidantsuch as 2,6-di-t-butyl-4-methylphenol,2,2-methylenebis(6-t-4-methylphenol),4,4-butylenebis(6-t-butyl-3-methylphenol),ethylenebis(oxyethylene)bis[3-(5-t-butyl-4-hydroxy-m-tolyl)propionate],octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate orpentaerythritoltetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate].The radical scavenger in the present invention may be a polymerizationinhibitor such as thiodiphenylamine, diethylhydroxylamine, hydroquinone,p-t-butylcatechol, 1,3,5-trihydroxybenzene or hydroquinone-methyl etheror an antioxidant such as 2,6-di-t-butyl-4-methylphenol,2,2-methylenebis(6-t-4-methylphenol),4,4-butylenebis(6-t-butyl-3-methylphenol),ethylenebis(oxyethylene)bis[3-(5-t-butyl-4-hydroxy-m-tolyl)propionate],octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate orpentaerythritoltetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate].

[0031] As the radical scavenger in the present invention, it ispreferred to use from 0 to 0.5 part by mass of the above-mentionedpolymerization inhibitor or from 0.1 to 1.5 parts by mass of theabove-mentioned antioxidant, per 100 parts by mass of chloroprene. Ifthe antioxidant is less than 0.1 part by mass, the increase of the gelcontent during the storage of the polychloroprene latex compositioncannot be suppressed, whereby the initial bond strength and the waterresistant bond strength will deteriorate.

[0032] In the present invention, the method for adding the radicalscavenger is not particularly limited. However, a method of adding theradical scavenger as dissolved in the chloroprene monomer to thechloroprene polymer, followed by removing the monomer by deaeration, ora method of adding the radical scavenger as emulsified by an addition ofe.g. a surfactant, to the chloroprene polymer, is preferred inconsideration of the dispersed state of the radical scavenger in thepolychloroprene latex composition.

[0033] The catalyst to be used for the polymerization of polychloropreneof the present invention, may, for example, be an inorganic peroxidesuch as potassium persulfate, or an organic peroxide such as a ketoneperoxide, a peroxyketal, a hydroperoxide, a dialkyl peroxide or a diacylperoxide. It is preferred to use potassium persulfate as the catalyst tocarry out the polymerization in a stabilized condition. Further, it ispreferred to use potassium peroxide in the form of an aqueous solutionhaving a concentration of from 0.1 to 5 mass %.

[0034] In order to increase the activities of the catalyst to be usedfor the polymerization of the polychloroprene latex of the presentinvention, sodium sulphite, potassium sulphite, ferrous sulfate, sodiumanthraquinone β-sulfonate, formamidine sulfonic acid or L-ascorbic acidmay, for example, be added.

[0035] The tackifier resin in the present invention may, for example, bea rosinate resin, a terpene phenol resin, a coumarone-indene resin, analiphatic hydrocarbon resin or an aromatic resin. As the tackifierresin, an emulsion of a terpene phenol resin or rosinate resin ispreferred to obtain the initial bond strength or the water resistantbond strength of the adhesive composition.

[0036] The amount of the tackifier resin is preferably from 20 to 150parts by mass, particularly preferably from 30 to 100 parts by mass, per100 parts by mass of the polychloroprene latex. If it is less than 20parts by mass, the initial bond strength and the water resistant bondstrength tend to be low, and if it exceeds 150 parts by mass, formationof the adhesive coating film tends to be impaired, whereby the bondstrength tends to be low.

[0037] The metal oxide in the present invention may, for example, bezinc oxide, titanium oxide or iron oxide. Zinc oxide or titanium oxideis preferred in order to improve the water resistance of the adhesivecomposition, and it is particularly preferred to use zinc oxide.

[0038] The amount of the metal oxide is preferably from 0.2 to 8.0 partsby mass, particularly preferably from 0.5 to 6.0 parts by mass, per 100parts by mass of the polychloroprene latex. If it is less than 0.2 partby mass, the water resistant bond strength of the adhesive compositionmay sometimes be inadequate, and if it exceeds 8.0 parts by mass, thebond strength in a normal state tends to deteriorate.

[0039] To the adhesive composition of the present invention, a curingaccelerator such as isocyanate or ethylene thiourea, an inorganic fillersuch as calcium carbonate, silica, talc or clay, a plasticizer orsoftener such as dibutyl phthalate or process oil, a thickener such assodium polyacrylate, water-soluble polyurethane or methyl cellulose, asurfactant such as a polyoxyalkylene alkyl ether, a 1:2 mol typealiphatic alkanolamide, a 1:1 mol type diethanolamide or apolyoxyethylene stearate, a film-formation assistant agent such aspropylene glycol n-butyl ether, dipropylene glycol n-butyl ether ortripropylene glycol n-butyl ether, an antifungal agent, a dyestuff,various antioxidants, an ultraviolet absorber, an antioxidant, etc. mayoptionally be incorporated, as the case requires.

[0040] The adhesive of the present invention is prepared by mixing thepolychloroprene latex, the tackifier resin, the metal oxide, etc. Themixing apparatus is not particularly limited, and a known apparatus suchas a three one motor, a homogenizer, a media mill or a colloid mill maybe used.

[0041] Coating of the adhesive of the present invention is notparticularly limited, but is preferably carried out only on the porousorganic material side. As a method for coating the adhesive to theporous organic material, automated mechanical coating capable of uniformcoating, is preferred, but the coating method is not particularlylimited. Usually, a method such as brush coating, troweling, spraycoating, roll coater coating or bar coater coating may be used.

[0042] The laminated product of the present invention can be obtained bycoating the adhesive on the porous organic material, laminating a cloththereon, followed by press bonding by a press machine. Such a bondingand laminating method is not particularly limited. In a case where theviscosity of the adhesive is low, it is preferred to introduce apreliminary drying step prior to laminating a cloth after coating theadhesive on the porous organic material.

[0043] By the preliminary drying machine, it is possible to preventoozing out of the adhesive from the cloth during pressing. Thepreliminary drying temperature is preferably from 50 to 80° C., morepreferably from 60 to 80° C. If it is higher than 80° C., the porousorganic material is likely to undergo thermal deformation before thepressing step. Further, the coating of the adhesive and lamination, maybe followed by drying at from 100 to 140° C. and then by press bondingby a press machine.

[0044] The pressing method may be hot pressing or cold pressing. In thehot pressing, a temperature of from 100 to 130° C. is preferred. In thecase of cold pressing, a step of heating the porous organic materialhaving the cloth mounted thereon at a temperature of from 100 to 130° C.is required prior to the pressing. The pressure in the pressing step isnot particularly limited and may be set depending upon the particularpurpose and application. In order to secure an adequate bond strengthwithout damaging the porous organic material of the laminate, it ispreferably from 0.05 to 10 MPa, more preferably from 0.1 to 6 MPa. Inthe pressing step, shaping depending upon the particular purpose orapplication can be carried out by a method of pressing the softenedsheet by heat, such as a free drawing method, a matched mold formingmethod, a plug and ring forming method, a slip forming method (drawforming method), a vacuum forming method or a compression moldingmethod.

EXAMPLES

[0045] Now, the present invention will be described with reference toExamples, but the present invention is by no means restricted by theseExamples. Further, in the following Examples, “parts” and “%” are basedon mass unless otherwise specified.

Example 1

[0046] Production of a Polychloroprene Latex

[0047] Using a reactor having an internal capacity of 30 liters, 94parts by mass of water and 3.5 parts by mass of polyvinyl alcohol (DENKAPOVAL B-05, saponification degree: 88 mol %, polymerization degree: 550)were put, heated (60° C.) and dissolved in a nitrogen stream. Thisaqueous solution was cooled to near room temperature, and then, 99 partsby mass of a chloroprene monomer, 1.0 part by mass of methacrylic acidand 0.3 part by mass of octylmercaptan were added thereto.

[0048] While maintaining this at 45° C., polymerization was carried outby using sodium sulphite and potassium persulfate as initiators toobtain a polychloroprene latex. The final polymerization rate was 99.5%.

[0049] Then, to this polychloroprene latex, a 10% sodium carbonateaqueous solution was added to adjust the PH, and then, 3 parts of a 20%aqueous solution of an aliphatic alkanolamide (manufactured by DIAMONDSHAMROCK CHEMICAL COMPANY) and 0.5 part by mass of a radical scavenger(Cellosol H633, manufactured by Chukyo Yushi Co., Ltd.; one obtained byemulsifying 2,6-di-t-butyl-4-methylphenol) were added to obtain latex Ahaving the solid content adjusted to 47%.

[0050] Then, with respect to this polychloroprene latex, the followingmeasurements were carried out.

[0051] Measurement of the Gel Content

[0052] The polychloroprene latex sample was freeze-dried and accuratelyweighed to obtain A. It was dissolved in toluene (adjusted to 0.6%), andusing a centrifugal separator and further using a metal net of 200 mesh,the gel was separated. The gel content was air-dried and then dried inan atmosphere of 110° C. for one hour and accurately weighed to obtainB.

[0053] The gel content was calculated in accordance with the followingformula.

Gel content=B/A×100(%)

[0054] The result was 38%.

[0055] Measurement of the pH

[0056] The latex sample was adjusted to 20° C. in a constant temperaturewater tank, whereupon the pH was measured by a pH meter. The pH was 7.5.

[0057] Production of an Adhesive

[0058] 100 parts by mass of polychloroprene latex A, 70 parts by mass ofa terpene phenol resin (Tamanol E-100, manufactured by Arakawa ChemicalIndustries, Ltd.) and 1 part by mass of zinc oxide (AZ-SW, manufacturedby OSAKI INDUSTRY CO., LTD.) were stirred by a three one motor toprepare adhesive A.

[0059] Further, adhesive A was coated on a foamed EVA sheet (2A-1064,manufactured by MITSUFUKU INDUSTRY CO., LTD., thickness: 5 mm) by abrush. The amount of adhesive A coated was 80 g (wet)/m². The coatedfoamed EVA sheet was dried at 70° C. for one minute to form an adhesivelayer, and a polyester cloth was overlaid thereon, followed by pressbonding under a pressure of 1 MPa by a press machine heated to 120° C.to obtain laminated product A. The process from this coating to thebonding will be referred to as bonding method A.

[0060] The laminated product was evaluated by the following methods.

[0061] Initial Bond Strength

[0062] Upon expiration of 10 minutes from the press bonding, the 180° C.peel strength was measured by a tensile tester at a speed of 200 mm/min.

[0063] Bond Strength in a Normal State

[0064] Upon expiration of five days from the press bonding, the 180° C.peel strength was measured by a tensile tester at a speed of 200 mm/min.

[0065] Water Resistant Bond Strength

[0066] Upon expiration of one day from the press bonding, the sample wasimmersed in pure water at 23° C. for 2 days, whereupon the 180° C. peelstrength was measured by a tensile tester at a speed of 200 mm/min.

Example 2

[0067] In Example 1, 100 parts by mass of latex A, 70 parts by mass of arosinate resin (SK-90D, manufactured by Harima Chemicals, Inc.), 1 partby mass of zinc oxide (AZ-SW, manufactured by OSAKI INDUSTRY CO., LTD.)and 2 parts by mass of ethylenethiourea (Axel-22S, manufactured byKawaguchi Kogyo K.K.) were stirred by a three one motor to prepareadhesive B. Adhesive B was coated on a foamed EVA sheet (2A-1064,manufactured by MITSUFUKU INDUSTRY CO., LTD., thickness: 5 mm) by abrush, followed by bonding by bonding method A to obtain laminatedproduct B.

Example 3

[0068] Adhesive A was coated on a foamed EVA sheet (2A-1064,manufactured by MITSUFUKU INDUSTRY CO., LTD., thickness: 5 mm) by abrush. The amount of adhesive A coated was 80 g (wet)/m². The coatedfoamed EVA sheet was dried at 70° C. for one minute to form an adhesivelayer, and a polyester cloth was overlaid thereon, followed by pressbonding under a pressure of 1 MPa by a press machine at roomtemperature, to obtain laminated product C. The process from coating ofthe adhesive to the bonding will be referred to as bonding method B.

Comparative Example 1

[0069] In the same manner as in Example 1 except that the chloroprenemonomer was 95 parts by mass and methacrylic acid was 5.0 parts by mass,latex B having a solid content of 47% was obtained.

[0070] The pH of latex B was 8.0, and the gel content was 45%.

[0071] 100 parts by mass of polychloroprene latex B, 70 parts by mass ofa terpene phenol resin (Tamanol E-100, manufactured by Arakawa ChemicalIndustries, Ltd.) and 1 part by mass of zinc oxide (AZ-SW, manufacturedby OSAKI INDUSTRY CO., LTD.) were stirred by a three one motor to obtainadhesive C.

[0072] Adhesive C was coated on a foamed EVA sheet (2A-1064,manufactured by MITSUFUKU INDUSTRY CO., LTD., thickness: 5 mm) by abrush, and by bonding method A, laminated product D was obtained.

[0073] With respect to the laminated products obtained in Examples 1 to3 and Comparative Example 1, the initial bond strength, the bondstrength in a normal state and the water resistant bond strength wereevaluated by the above-described methods, and the results are shown inTable 1.

[0074] In Examples 1 to 3, the bond strength was so high that thematerial underwent cohesive failure at the time of the measurement, andno numerical value was obtained. TABLE 1 Comparative Example 1 Example 2Example 3 Example 1 Laminated Laminated Laminated Laminated Laminatedproduct product A product B product C product D Adhesive AdhesiveAdhesive Adhesive Adhesive Type A B A C Bonding Bonding Bonding BondingBonding method method A method A method B method A Bond strength (N/mm)Initial Cohesive Cohesive Cohesive Cohesive bond failure failure failurefailure strength Bond Cohesive Cohesive Cohesive Cohesive strengthfailure failure failure failure in a normal state Water CohesiveCohesive Cohesive 0.5 resistant failure failure failure bond strength

INDUSTRIAL APPLICABILITY

[0075] As is evident from Table 1, the laminated product of the presentinvention is excellent in the initial bond strength, the bond strengthin a normal state and the water resistant bond strength and is thususeful as a component required to have impact absorption, of furniture,bed clothes, interior parts of automobiles, shoe materials, etc.

1. A laminated product having a porous organic material and a clothbonded with an adhesive comprising, as major ingredients, apolychloroprene latex which is obtained by polymerizing 100 parts bymass of chloroprene with more than 0 part by mass and less than 2 partsby mass of an ethylenically unsaturated carboxylic acid in the presenceof from 0.5 to 4 parts by mass of a polyvinyl alcohol and then adding apH adjustor and a radical scavenger and which has a gel content in thechloroprene polymer of from 10 to 60 mass % and a pH of from 6 to 10, atackifier resin and a metal oxide.
 2. The laminated product according toclaim 1, wherein the polyvinyl alcohol has a saponification degree offrom 75 to 90 mol %.
 3. The laminated product according to claim 1 or 2,wherein the metal oxide is zinc oxide or titanium oxide.
 4. Thelaminated product according to any one of claims 1 to 3, wherein theporous organic material is a foamed ethylene/vinyl acetate copolymer. 5.The laminated product according to any one of claims 1 to 4, wherein theethylenically unsaturated carboxylic acid is acrylic acid or methacrylicacid.
 6. The laminated product according to any one of claims 1 to 5,wherein the polychloroprene latex has a solid content concentration offrom 40 to 65 mass %.
 7. The laminated product according to any one ofclaims 1 to 6, wherein the radical scavenger is a polymerizationinhibitor or an antioxidant, and from 0 to 0.5 parts by mass of thepolymerization inhibitor or from 0.1 to 1.5 parts by mass of theantioxidant, is used per 100 parts by mass of the chloroprene.
 8. Thelaminated product according to any one of claims 1 to 7, wherein thetackifier resin is a terpene phenol resin or a rosinate resin and isadded in an amount of from 20 to 150 parts by mass per 100 parts by massof the polychloroprene latex.
 9. A bonding method which comprisesbonding a porous organic material and a cloth with an adhesivecomprising, as major ingredients, a polychloroprene latex which isobtained by polymerizing 100 parts by mass of chloroprene with more than0 part by mass and less than 2 parts by mass of an ethylenicallyunsaturated carboxylic acid in the presence of from 0.5 to 4 parts bymass of a polyvinyl alcohol and then adding a pH adjustor and a radicalscavenger and which has a gel content in the chloroprene polymer of from10 to 60 mass % and a pH of from 6 to 10, a tackifier resin and a metaloxide.
 10. The bonding method according to claim 9, wherein the bondingis carried out by coating the adhesive only on the porous organicmaterial side.